Alkylation



Dec. 10, 1963 T. HuTsoN, JR

ALKYLATION 2 Sheets-Sheet 1 Filed June 27. 1960 INVENTOR. THOMAS HUTSON, JR.

A TTORNEYS Dec. 10, 1963 T. HuTsoN, .JR 3,113,987

ALKYLATION Filed June 27, 1960 2 Sheets-Shea?I 2 United States Patent 3,113,987 ALKYLAHGN Thomas Hutson, lr., Bartlesville, Ghia., assigner to Phillips Petroleum Company, a corporation of Delaware Filed lune 27, i960, Ser. No. 38,9% 6 Claims. (Ci. Zeil-@$3.43)

This invention relates to alkylation. ln one of its aspects, the invention relates to the Ialkylation of an alkylatable compound with each of at least two oleins by passing said compound and one of said oleins into an alkylation zone in which alkylation ensues in the presence of a liquid `alkylation catalyst at a temperature at which the last-mentioned olelin is optimally alkylated and wherein the other of said oletins is passed into an alkylation zone together with a further quantity of said isoparain and therein alkylated in the presence of a further quantity of said :alkylation catalyst at a temperature `at which the last-mentioned olefin is optimally alkylated and wherein the contents of said -alkylation Zones are combined after completion of the respective alkylations and alkylation catalyst separated from the combined eilluents, `a portion of the catalyst being returned for reuse in each of said alkylation zones while the combined talkylate from which the acid has been separated is fractionated in a common fractionation zone. In another of its aspects, the invention, in one embodiment, separately alkylates isobutane in one zone with a butylene and in another zone with propylene at temperatures at which said oletins optimally alkylate isobutane, the liquid allrylation catalyst comprising essentially' hydrofluoric `acid alkylation catalyst or its equivalent. In a still further aspect, the invention relates to a method of converting an existing alkyl-ation unit or system having but one alkylation zone into a system which will produce improved product by simplf,r adding to said system one more alkylation zone and utilizing the existing catalyst settling zone and fractionation zone for separating the alkyla-tion effluents from acid and fractionating the alkylate thus produced. ln a further aspect of the invention, it relates to reducing the separating time required in an alkylation in which at least two alkylations are separately conducted at ditferent temperatures in the presence of `a liquid catalyst, which is separated from the alkylate produced by settling or `an equivalent operation, by -admixing the second alkylation effluent obtained prior to the separation operation.

The alkylation of an isoparaiiin with one or more oleiins in la single -alkylation zone, using various acidic catalysts, for example, HF, is conventional in the art. Where mixed oleiins are reacted in a single alkylation zone, advantage cannot be taken of different optimum temperatures `and other 'conditions for the individual olens present. Of course, a mixture of o-leiins could be fractionated into its constituents, `and these constituents run consecutively through the alkylation plant, or run through separate complete plants. However, these procedures, while solving the problem of controlling optimum alkylation conditions, introduce other problems of scheduling and expense of equipment. Thus, it is old in the art to separately alkylate different olelins `and, when this has been done, it has been the standard practice to provide separate settlers for each alkylation zone.

lt has now occurred to me that there is really no need to continue to provide a separate alkylation effluent acid settler or separation zone or, for that matter, any further separate equipment and that only the alkylation reaction zone need be kept separate for each of the different oleiinic feeds. That is, the rest of the equipment, namely, the acid settler, HF purification equipment, product purication towers, etc., can be used in common. Thus, except for an olefin fractionating facility and multiple alkylation reactors, the existing or conventional plant equip- Patented Dec. l0, 'i953 ment can be used. By so operating, the quality and yield of alkylate is increased lat only a slight increase in the cost of equipment or in the cost of altering existing equipment.

Further, it is noted that the combination of the two streams of alkylate reduces the temperature of the higher temperature obtained alky-late, thus improving the settling rate or separation of .the acid catalyst used.

lt will be obvious to one skilled in the art in possession of this disclosure that the modus operandi and/ or processes disclosed can be applied to alkylations other than those specifically `set forth in the description here made.

lt is an object of this invention to provide an alkylation process. it is a further object of this invention to provide an improved alkylation process or method using existing equipment so modied that optimal alkylation of diiferent olefinic materials can be practiced in the presence of a liquid alkylation catalyst. It is a further object of this invention to provide ra process for the alkylation of an isoparallin with at least twoseparate and ditferent o-lenic stocks at temperature-s which are best suited for each of said stocks, the alkylations being eifected simultaneously' in vconventional equipment which has been altered only to Ian irreducible extent. A still further object of the invention is to alkylate, say, isobutane with a butylene, isobutane with amylenes and isobutane with propy'lene in the presence of hydroiluoric acid in a manner such that each of the olciins will optimally alkylate isobutane and to accomplish these results by providing to existing equipment or to `an existing system an irreducible additional amount of equipment. Another object of the invention is to provide more rapid separation of liquid catalyst from alkylation eluents with consequent savings of the amount of equipment required for subsequent treatment. A further object is to provide a modus-operandi in which catalyst carry-over from the separation step is reduced, thus reducing the extent of treatment required to obtain a final desired product alkylate.

Other aspects, objects and the several advantages of this invention are `apparent from a study of this disclosure, the drawing and the appended claims.

According to this invention, there is provided a process for the `alkylation of a compound alkylatable with olefin which comprises separating a mixture of oletins into at least one olen which will alkylate said compound optimally at a rst temperature in the presence of a liquid catalyst and into another olen which will alkylate said compound optimally at a second dierent temperature in the presence of said catalyst, preparing a first alkylation feed comprising said one olen and said compound and subjecting said irst feed in a iirst zone to alkylation conditions including said first temperature, prepa-ring a second Ialkylation feed comprising said another oleiin and said compound and subjecting said second feed in a second Zone to alkylation conditions including said second different temperature, obtaining and removing from said iirst and second Zones, respectively, alkyl-ate containing effluent also containing said liquid catalyst, passing said eiiiuent to a common liquid catalyst separating zone, separating liquid catalyst fromfsaid combined etlluents in said separating zone, returning at least a portion of said catalyst to each of said first and second zones and recovering a combined alkylate from said separating zone.

Referring now to the drawing, FIGURE 1 shows separate alkylation of propylene and butylenes according to the invention. FIGURE 2 shows alkylation of a (Z3-C., olen feed, i.e., a mixed olen feed. FIGURE 2 depicts a conventional operation here included `for purposes of comparison.

Referring now to FEGURE l, according to the invention, a CVC, olefin feed, that is, a feed containing propylene and butylenes, is passed by l to column 2 wherein ice passed by 6 to butylene reactor 7 which is maintained at 5 about 60 F. and wherein the isobutane and butylene undengo alkylation in the presence of HF catalyst which' enters by 8. Alkylation effluent and acid pass by way of pipe 9 to settler 10. Propylene concentrate is passed into reactor 11 in which it is alkylated with isobutane also passed into reactor 111 by way of i12 using catalyst which is passed to reactor 11 by Way of 13. Eluent from. reactor 1\1 passes by 14 to settler 10. ln the settler, acid is settled from the combined eiiiuents and removed therefrom by way of 15 and passed to 8 and 13 and ultimately 1 by `way of 8 and 13 to reactors 7 and 11. When desired, a portion of used acid lis taken off at 16 and passed to rerun according to practices known in the art. Aikylate is passed by -way of 17 to deisobutanizer column 18 which is operated as will be understood by those skilled in this ant. The operation of this column does not form a part of this invention. Isobutane is taken overhead by way of 19 and accumulator 20 and a portion thereof is passed by pipe 21 and pipe 22 to the column as redux, the remainder passing by way of pipe 5 and pipes 6 and 12 to reactors 7 and 1d, respectively, as already described. Bottoms -frorn column 18 constitute largely alkylate and normal butane and are passed by pipe 23 to stabilizer 24 from which a normal butane concentrate is obtained at 25 and the alkylate removed at 26. A stream containing propane and HF is passed by pipe 27 .to depropanizer column 28 from which some isobutane is removed at 29 and passed into pipe 5 for reuse, as already described. Overhead from column 28 passes by Way of accumulator 30 =to HF stripper 31 .from the bottom of which propane is recovered at 32. HF is recovered at 33 at the foot of the accumulator. This HF can be reused, as desired.

Referring now to FIGURE 2, it is at once seen that only yone reactor is provided vand that, therefore, the olefin feed which is necessarily mixed is passed directly by way of pipe to reactor 41, together with isobutane supplied at 42 and alkylation acid catalyst supplied at 43. Alkylation effluent, including the acid, passes by 44 to settler 45 from which settled acid is recycled by way lof 46 and 4 43, together with make-up HF, as known in the art, supplied at 47. The hydrocarbon phase passes by 48 to deisobntanizer 49 lfrom which alkylate and normal butane passes by 50 to stabilizer 51 from the bottom of which stabilized alkylate is removed at 52 and a normal butane concentrate is removed overhead at 53. Overhead from the deisobutanizer is essentially processed as described in connection with FIGURE 1 and isobutane is passed by way of '5d to pipe 42 for reuse.

The individual alkylations which are embodied according to the concept of this invention into the combination of steps which constitute the invention are not considered to be a par-t of this invention, except as included in said combination. Thus, the conditions tof operation in the 5 several reactors of FIGURE l are already known.

Gener-tally, the ratio of isoparain to olen will lie in the range of about 4 to about 25 and preferably will be in the operation of this invention about l2. To obtain a composite of alkylate which is now preferred according to the invention, fit is preferred according to the invention that about l0 to 60 percent of the olens used be propylene and the remainder be butylenes. Accordingly, in modifying existing equipment, the added reactor will be chosen bearing this in mind. Depending upon overall throughput, the chosen reactor will either be the smaller or the larger in the case of two oieiins, as the case may be.

The catalyst is also well known in the art. Generally, the catalyst now preferred will be -92 percent by weight HF, with a water content not to exceed more than about 0.5 percent and an acid soluble oil content not to substantially leave the range 0.1-1 percent, the remainder being dissolved hydrocarbons. The HF recycle rate will be in the approximate range of .25 to S or so volumes of HF per volume of hydrocarbon.

The reaction time will be governed by the nature of the equipment used. ln general, this time of reaction Will be in the range of 20 seconds to 40 seconds to 5 to 20 minutes, depending upon the type of alkylation reactor employed. Example I A run was made according to the invention in an array of apparatus as shown in FIGURE 1. The constitution of the streams shown in FlGURE 1, and the properties of the -alkylate obtained are as follows:

Make- Make- Oletln Propyl- Butylup up Isobu- HF Pron-bu- Feed, ene enc Isobu- HF, tane Repane, tane Wt. Conc., Conc., tane, Wt. Recycle, Mol Conc., Percent Wt. Wt. Percent cycle, Wt. Percent Wt.

Percent Percent Percent Wt. Percent Percent Percent Olens (48.6) (77. O) (40. 5) Lb./Hr 7.31 1. 72 5. 59 3. 91 0. 7 43. 7 182 1. 59 2. 23

Alkylate AP Gravity 70. 2 Rcid Vapor Pressure, p s i 4.0 Initial Boiling Point, F 120 l0 185 507 222 90%. 289 End Point.- 430 Research Octane No. and 3 TEL 105. 5 Motor Octane No. and 3 TEL.-. 107.0 14h/Er 7. 40

Alkylate/Olen (volume) =1.73.

Example l1 For comparison, an alkylation was made with mixed olefins in a single reactor, in apparatus depicted in FIG- URE 2. The constitution of the streams shown in FIG- 6 Reasonable variation and modification are possible within the scope of the foregoing disclosure, the drawing and the appended claims to the invention, the essence of which is that, by providing a separate reactor for separate URE 2, and the properties of the alkylate obtained are 5 aikylation of olefins in an existing system, alkylation with as follows: a common liquid alkylation catalyst can be effected using Make- Oletn up Isobu- Make- DeC3 n-bu- Pro- Re- Fecd, Isobutane up BTMS, tane pane, cycle Wt. tane, Re- HF, Mol Conc., Mol Percent Wt. cycle, Wt, Percent Wt, Percent Wt.

Percent Wt. Percent Percent Percent Percent Allrylate API Gravity 0s. e Reid Vapor Pressure, n s i 3. 43 Initial Boiling Point, F 135 9097 323 End Point 438 Research Octane No. and 3 TFL 102. 9 Motor Octane No. and 3 TEL 105.0 L11/nr 7. se

Alkylate/Olen (volume) =1.69.

By comparison of Example I with Example II, it will the existing acid separation and alkylate fractionation be seen that :the method of the invention lproduces an and recovery zone. increase in the Research Octane No. of 21.6 and an 1 claim: increase in Motor Octane No. of 2.0, together with l. A process for the alkylation of a compound alkylsmall increases in API Gravity, Reid Vapor Pressure F atable with an olefin which comprises separating a mixture and yield. Very little additional plant equipment is rei of olefins into at least one olefin which will alkylate said quired to obtain these advantages. compound optimally at a first temperature in the presence Although in the example, essentially the olefin and isoof a liquid catalyst and into another olefin which will paramn there shown have been alkylated, it is `Within the alkyiate said compound optimally at a second different scope of the invention to adapt it to other feeds. Such r temperature in the presence of said catalyst, preparing feeds advantageously can include amylenes and/or iso- J0 a first alkylation feed comprising said one olefin and said pentanes or isopentane can be alkylated with various compound and subjecting said first feed in a first zone to amylenes. Other operations will be evident to one skilled alkylation conditions including said first temperature, prein the art in possession of this disclosure when he has paring a second alkylation feed comprising said another studied the same, olefin and said compound and subjecting said second Although the invention is now preferred to be operated 5D feed separately and apart from said first feed and alkylate using catalyst as earlier set forth and defined, boron uoresulting therefrom in a second zone to alkylation condiride containing catalyst or a catalyst consisting essentially tions including said second different temperature, obtainof liquid phase EP3 are Within the scope of the invention, ing and removing from said first and second zones, reas may be other catalysts as these are or may become spectively, the several alizylate containing effluents also available, it being obvious that the invention is in the 69 containing said liquid catalyst, passing said effluents to a combination of steps as set forth in one or more claims common liquid catalyst separating zone, separating liquid and not in the catalyst employed. Thus, sulfuric acid catalyst from said combined eiuents in said separating might Weil be used provided suitable changes appropriate zone, returning at least a portion of said catalyst to each to this catalyst, which one skilled in the art will underr of said first and second zones and recovering a combined stand having read this disclosure, are made. Similarly, 69 alkylate from said separating zone. the alumnium chloride complex can be adapted but is 2. A process according to claim l wherein said comnot now preferred. pound is isobutane.

When alkylating an isoparaiiin, a somewhat higher ratio 3. A process vfor the alltylation of an isoparaffin with of isoparaflin to olefin can be employed to advantage. each of a buty-lene and propylene in the presence of a Temperature ranges for the various olefins as these can 79 liquid .alkylation catalyst which comprises subjecting in be alkylated using the present invention are as follow: a first Zone an alkylation feed 0f isoparaffin and a butylene to alkylation conditions including a temperature at Propylene-100 to 150 F.; preferred 110 to 130 F. which a butylene optimally alkylates said isoparafiin and Butylenes-40 to 90 F.; preferred 50 to 60 F. said catalyst, subjecting in a second zone another alkyla- Amy1enes-25 to 75 F.; preferred 40 to 50 F. 75 tion feed of isoparafn and propylene separately and apart from said feed of isoparan and butylene and alkylate resulting therefrom to alkylation conditions including a temperature at which propylene optimally alkylates said isoparain and said catalyst, passing the several alkylation 'ei'lluents containing said catalyst from said rst and second zones to a common liquid catalyst separation zone, separating liquid catalyst from said efliuents in said Zone, returning at least a portion of said catalyst to each of said first and second zones and recovering a combined alkylate from said separating zone.

4. A process according to claim 3 wherein the isoparan is isobutane.

5. A process according to claim 3 wherein the temperature at which the propylene containing feed is alkylated in the presence of said catalyst is of the order of 125 F. and the temperature at which said butylene is alkylated is of `the order of about 60 F. and the liquid catalyst is hydrouoric acid.

6. A method of increasing the octane number obtainable with a' single alkylation zone containing system which comprises providing an additional alkylation zone in said system, fractonating an oletnic feed into at least one olefin which will alkylate optimally an isoparain at a irst temperature in the presence of a liquid catalyst and into at least one other olen which will alkylate said isoparafn optimally at a second diteren-t temperature in presence of said catalyst, preparing a first alkylation taining said catalyst from said iirst and second zones,

passing said effluents to a common liquid catalyst separating zone, separating liquid catalyst from said combined effluents in said separating zone, returning at least a portion of `said catalyst to each of said first and second zones and recovering a combined alkylation eluent from said separating zone.

References Cited in the le of this patent UNITED STATES PATENTS 2,356,374 Blount Aug. 22, 1'944 2,415,717 Watkins et al Feb. 111, 1947 2,417,251 Hemminger Mar. l1, 1947 2,438,852 Goldsby et al Mar. 30, 1948 2,476,750 Matuszak July 19, 1949 2,820,073 Dixon et al. Jan. 14, 1958 

1. A PROCESS FOR THE ALKYLATION OF A COMPOUND ALKYLATABLE WITH AN OLEFIN WHICH COMPRISES SEPARATING A MIXTURE OF OLEFINS INTO AT LEAST ONE OLEFIN WHICH WILL ALKYLATE SAID COMPOUND OPTIMALLY AT A FIRST TEMPERATURE IN THE PRESENCE OF A LIQUID CATALYST AND INTO ANOTHER OLEFIN WHICH WILL ALKYLATE SAID COMPOUND OPTIMALLY AT A SECOND DIFFERENT TEMPERATURE IN THE PRESENCE OF SAID CATALYST, PREPARING A FIRST ALKYLATION FEED COMPRISING SAID ONE OLEFIN AND SAID COMPOUND AND SUBJECTING SAID FIRST FEED IN A FIRST ZONE TO ALKYLATION CONDITIONS INCLUDING SAID FIRST TEMPERATURE, PREPARING A SECOND AKYLATION FEED COMPRISING SAID ANOTHER OLEFIN AND SAID COMPOUND AND SUBJECTING SAID SECOND FEED SEPARATELY AND APART FROM SAID FIRST FEED AND ALKYLATE RESULTING THEREFROM IN A SECOND ZONE TO ALKYLATION CONDITIONS INCLUDING SAID SECOND DIFFERENT TEMPERATURE, OBTAINING AND REMOVING FROM SAID FIRST AND SECOND ZONES, RESPECTIVELY, THE SEVERAL ALKYLATE CONTAINING EFFLUENTS ALSO CONTAINING SAID LIQUID CATALYST, PASSING SAID EFFLUENTS TO A 